Crosslinkable composition and method of producing the same

ABSTRACT

The instant invention provides a crosslinkable aqueous composition, method of producing the same, crosslinked compositions, and method of producing the same. The crosslinkable composition comprising: an aqueous dispersion comprising; (a) water; (b) a polycarbamate comprising at least an average of 2.0 carbamate functional groups; (c) a polyaldehyde comprising at least two aldehyde groups; (d) an acid catalyst; and (e) optionally one or more surfactants; wherein said aqueous dispersion has a pH in the range of less than 7; and wherein said composition is capable of being crosslinked at a temperature in range of less than 80° C. upon substantial removal of water.

FIELD OF INVENTION

The instant invention relates to a crosslinkable aqueous composition,method of producing the same, crosslinked compositions, and method ofproducing the same.

BACKGROUND OF THE INVENTION

Low molecular polymers (Mn of 500-10,000) containinghydroxyl-functionality (also referred to as polyols) are widely used incoating applications and are cured at room temperature or elevatedtemperatures using a variety of crosslinking technologies. The mosttypical crosslinkers are polyisocyanates and aminoplast resins.Polyisocyanate crosslinkers offer the advantages of low temperature cureand provide coatings with superior properties, but suffer from hightoxicity, high cost and the limitation of balancing pot life with drytime. Aminoplast resins are often used as crosslinkers because theyoffer a good balance of lower cost and good coating performance, butcuring at higher temperature is often required and they suffer from thetoxicity of residual formaldehyde.

Accordingly there is a need for a new crosslinking technology underambient conditions (or low temperature bakes, e.g. 60° C.). Furthermorethere is need for coating properties when coating compositions arecrosslinked while maintaining lower levels of toxicity.

SUMMARY OF THE INVENTION

The instant invention provides a crosslinkable aqueous composition,method of producing the same, crosslinked compositions, and method ofproducing the same.

In one embodiment, the instant invention provides crosslinkablecomposition comprising: an aqueous dispersion comprising; (a) water; (b)a polycarbamate comprising at least an average of 2.0 carbamatefunctional groups; (c) a polyaldehyde comprising at least two aldehydegroups; (d) an acid catalyst; and (e) optionally one or moresurfactants; wherein said aqueous dispersion has a pH in the range ofless than 7; and wherein said composition is capable of beingcrosslinked at a temperature in range of less than 80° C. upon removalof a substantial portion of water.

A crosslinked composition derived from the inventive crosslinkableaqueous composition comprising carbamate ester linkages prepared by thereaction of: (a) a polycarbamate comprising at least an average of 2.0carbamate functional groups; and (b) a polyaldehyde comprising at leasttwo aldehyde groups; in the presence of (c) an acid catalyst; and (d)optionally one or more surfactants; wherein said initial aqueousdispersion has a pH in the range of less than 7; and wherein saidcomposition is crosslinked at a temperature in range of less than 80° C.

In an alternative embodiment, the instant invention further provides aprocess for producing a crosslinkable composition comprising: (1)selecting a polycarbamate dispersion comprising (a) a polycarbamatecomprising at least an average of 2.0 carbamate functional groups, (b)water, and (c) an acid catalyst; (2) selecting a polyaldehyde comprisingat least two aldehyde groups; (3) contacting said polycarbamatedispersion with the polyaldehyde; (4) thereby forming an aqueousdispersion, wherein said aqueous dispersion has a pH in the range ofless than 7; (5) thereby producing said crosslinkable composition,wherein said crosslinkable composition is capable of being crosslinkedat a temperature in range of less than 80° C.

In another alternative embodiment, the instant invention furtherprovides a process for producing a crosslinkable composition comprising:(1) selecting a polycarbamate dispersion comprising a polycarbamatecomprising at least an average of 2.0 carbamate functional groups, andwater; (2) selecting a polyaldehyde comprising at least two aldehydegroups; (3) selecting an acid catalyst; (4) contacting saidpolycarbamate dispersion, polyaldehyde, and acid catalyst in thepresence of water; (5) thereby forming an aqueous dispersion, whereinsaid aqueous dispersion has a pH in the range of less than 7; (6)thereby producing said crosslinkable composition, wherein saidcrosslinkable composition is capable of being crosslinked at atemperature in range of less than 80° C.

In another alternative embodiment, the instant invention furtherprovides a coating layer derived from the inventive crosslinkablecomposition.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the crosslinkable composition is used as an adhesive,primer, sealant, caulk, stain, and/or filler.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the crosslinkable composition is applied to at least onesurface of a substrate such as metal, plastic, wood, concrete, asphalt,hair, paper, leather, glass, rubber, foam and/or textiles.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the aqueous dispersion has a pH in the range of less than 6,for example less than 5, or less than 4, or from 1 to 4, or from 2 to 4.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the polycarbamate is the condensation product of one or morepolyols with an unsubstituted carbamic acid alkyl ester or urea.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the polyol is an acrylic, styrene-acrylic,styrene-butadiene, ethylenevinylacetate, vinylacetate, vinyl, ester,urethane, alkyd, ether or carbonate polymer or oligomer thereof.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the polycarbamate has carbamate groups and hydroxyl groupsin a ratio of the equivalents of carbamate groups to the number ofequivalents of hydroxyl functional groups of from 1:10 to 20:1.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the polycarbamate is prepared through free radical emulsionor suspension addition polymerization of one or more α,β-ethylenicallyunsaturated monomers at least one of which comprises carbamatefunctionality.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the polyaldehyde has from 2 to 20 carbon atoms.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the polyaldehyde has greater than 20 carbon atoms, with theproviso that a polyaldehyde having greater than 20 carbon atoms has atleast one aldehyde group for every 30 carbon atoms.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the polyaldehyde is selected from the group consisting of(cis,trans)-1,4-cyclohexanedicarboxyaldehydes,(cis,trans)-1,3-cyclohexanedicarboxyaldehydes, glutaraldeyde, glyoxal,combinations thereof, and/or mixtures thereof.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the acid catalyst has a pKa of less than 6.0, for example apKa of less than 4.0.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the acid catalyst is a Lewis acid.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the composition further comprises a curing inhibitorcomprising alcohol.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the alcohol is selected from the group consisting ofethanol, 1-propanol, 1-butanol, 1-pentanol, Ethylene glycol monoalkylethers, diethylene glycol monoalkyl ethers, propylene glycol monoalkylethers and dipropylene glycol monoalkyl ethers,2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate, combinations thereof,and mixture thereof.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the carbamate functional group has a radical structure offormula of:

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the acid catalyst is a functional group which isincorporated into the backbone of the polycarbamate.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention provides a crosslinkable aqueous composition,method of producing the same, crosslinked compositions, and method ofproducing the same. The crosslinkable aqueous composition according tothe present invention comprises: an aqueous dispersion comprising; (a)water; (b) a polycarbamate comprising at least an average of 2.0carbamate functional groups; (c) a polyaldehyde comprising at least twoaldehyde groups; (d) an acid catalyst; and (e) optionally one or moresurfactants; wherein said aqueous dispersion has a pH in the range ofless than 7; and wherein said composition is capable of beingcrosslinked at a temperature in range of less than 80° C. upon removalof a substantial portion of the water.

The crosslinkable aqueous composition comprises up to 100 percent byweight of the aqueous dispersion, for example, from 10 to 100 percent byweight the aqueous dispersion, or in the alternative from 65 to 100percent by weight of the aqueous dispersion. The crosslinkable aqueouscomposition may further comprise one or more additional film forming ornon film forming polymers, extenders, emulsifiers, coalescing agents,plasticizers, antifreezes, curing agents, buffers, neutralizers,thickeners, rheology modifiers, humectants, wetting agents, biocides,anti-foaming agents, UV adsorbers, fluorescent brighteners, light orheat stabilizers, chelating agents, dispersants, tackifiers, colorants,waxes, water-repellants and pigments.

The aqueous dispersion comprises from 20 to 85 percent by weight ofwater, based on the weight of the dispersion; for example, the aqueousdispersion comprises from 30 to 75 percent by weight of water, based onthe weight of the aqueous dispersion. The aqueous dispersion comprises15 to 80 percent by total weight of solid content, based on the weightof the aqueous dispersion; for example, from 25 to 70 percent by weightof total solid content, based on the weight of the dispersion; or in thealternative, from 35 to 65 percent by weight of total solid contentbased on the weight of the aqueous dispersion. The aqueous dispersionhas a pH in the range of less than 7; for example, in the range of fromless than 6, or in the alternative, in the range of from less than 5, orin the alternative, in the range of from less than 4, or in thealternative, from 1 to 4, or in the alternative from 2 to 4. The aqueousdispersion has a viscosity in the range of from less than 10,000 cP, forexample, in the range of from less than 1,000 cP.

The aqueous dispersion has long term shelf stability, for example, theaqueous dispersion remains a stable dispersion for prolonged periods,e.g. at least for 30 days, while remaining suitable for its intendedpurpose. The aqueous dispersion has acceptable heat stability forroutine storage and transportation, for example, the aqueous dispersionis heat stable at 60° C. for a period of 10 days, while remainingsuitable for its intended purpose.

The aqueous dispersion comprises from 15 to 85 percent by weight of thepolycarbamate component, based on the weight of the dispersion; forexample, from 25 to 70 percent by weight of the polycarbamate component,based on the weight of the dispersion; or in the alternative, from 35 to65 percent by weight of the polycarbamate component, based on the weightof the dispersion. The polycarbamate component comprises a polycarbamatecomprising at least an average of 2.0 carbamate functional groups.Unless otherwise noted herein, the term “carbamate functional group”means a radical structure of formula

In one embodiment, the polycarbamate is the condensation product of oneor more polyols with an unsubstituted carbamic acid alkyl ester or urea.As used herein, the term “polyol” means an organic molecule having atleast 2-OH functionalities. In one embodiment, such polyol is anacrylic, styrene-acrylic, styrene-butadiene, ethylenevinylacetate,vinylacetate, vinyl, ester, e.g. polyester, urethane, alkyd, ether orcarbonate polymer or oligomer thereof. As used herein, the term“polyester polyol” means a subclass of polyol that is an organicmolecule having at least 2 alcohol (—OH) groups (preferably includingalpha,omega —OH) and at least one carboxylic ester (CO₂—C)functionality. The term “alkyd” means a subclass of polyester polyolthat is a fatty acid-modified polyester polyol wherein at least onecarboxylic ester functionality is preferably derived from anesterification reaction between an alcoholic —OH of the polyol and acarboxyl of a (C₈-C₆₀) fatty acid.

In one embodiment, the polycarbamate component can be produced via batchprocess or continuous process. In one embodiment, one or morepolycarbamates, which are optionally dissolved in a solvent, e.g.organic solvent, or in the alternative, melted via heat, and optionallyone or more surfactants, and water are fed into a mixer, e.g. an OAKSMixer or an IKA Mixer, thereby dispersing the one or more polycarbamatesinto the water, and thereby forming an aqueous polycarbamate dispersion.

In one embodiment, the polycarbamate has carbamate groups and hydroxylgroups in a ratio of the equivalents of carbamate groups to the numberof equivalents of hydroxyl functional groups of from 1:9 to 20:1. Inanother embodiment, the polycarbamate is prepared through free radicalemulsion or suspension addition polymerization of one or moreα,β-ethylenically unsaturated monomers at least one of which comprisescarbamate functionality.

The aqueous dispersion comprises from 0.5 to 15 percent by weight of thepolyaldehyde component, based on the weight of the total dispersionsolids; for example, from 0.5 to 10 percent by weight of thepolyaldehyde component, based on the weight of the dispersion; or in thealternative, from 1 to 5 percent by weight of the polycarbamatecomponent, based on the weight of the total dispersion solids. As usedherein, the term “polyaldehyde” means a molecule containing two or morealdehyde groups or their hydrates, or their acetals or hemiacetals,wherein the molecule is capable of reacting with the polycarbamatecomponent. As used herein, the phrase “react together” means creatingone or more covalent bonds between two or more molecules, or portionsthereof.

The aldehyde group can be written herein as —C(═O)H or —CHO. In anotherembodiment, the polyaldehyde has from 2 to 20 carbon atoms. In anotherembodiment, the polyaldehyde has greater than 20 carbon atoms, with theproviso that a polyaldehyde having greater than 20 carbon atoms has atleast one aldehyde group for every 30 carbon atoms. In one embodiment,the polyaldehyde is selected from the group consisting of(cis,trans)-1,4-cyclohexanedicarboxyaldehydes,(cis,trans)-1,3-cyclohexanedicarboxyaldehydes, glutaraldeyde, glyoxal,combinations thereof, and/or mixtures thereof. Exemplary polyaldedyes,e.g. glutaraldeyde, are commercially available under the trade nameUCARCIDE™ 42 available from The Dow Chemical Company. Other exemplarypolyaldedyes, e.g. glyoxal, are commercially available from BASF.

The crosslinkable composition of the present invention is mixed toprepare the ambient temperature curable composition of the presentinvention. The methods of using the ambient temperature curablecomposition of the present invention are useful for preparing thecrosslinked compositions of the present invention. The crosslinkedcompositions of the present invention are useful as a coating, adhesive,primer, sealant, caulk, stain or filler. The adhesive, coating, orsealant of the present invention is useful for preparing an articlecomprising the same.

The crosslinkable compositions of the present invention have a highdegree of crosslinking and, one or more other improved properties suchas, for example, improved water resistance, improved chemicalresistance, improved deterioration resistance to methyl ethyl ketone(MEK) rubs, increased hardness, improved cross-hatch adhesion, or acombination thereof. The only byproduct produced as a result of thecuring step is water. As used herein, the term “byproduct” means asubstance or molecule that is produced from a reaction as a naturalconsequence of the intended chemical transformation (e.g., release of amolecule of water in a chemical transformation involving a dehydration).In contrast, the term “side product” means an unintended substance ormolecule that is produced from a reaction (e.g., due to a side reactionbetween two or more molecules of one of the reactants of a reactionemploying two or more different reactants or due to decomposition of areactant or product). These advantages mean that the invention can beemployed in low temperature curing commercial applications thatheretofore were unattainable by prior art approaches, which producedunsuitably low levels of crosslinking, unacceptable levels of volatileorganic compound (VOC) byproducts, or both, and/or required unsuitablyhigh curing temperatures.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same coating layers and adhesives made therefrom, andmethod of making such articles, in accordance with any of the precedingembodiments, except that the polycarbamate has carbamate groups andhydroxyl groups in a ratio of the equivalents of carbamate groups to thenumber of equivalents of hydroxyl functional groups of from 1:9 to 20:1.

The aqueous dispersion can be formed by any number of methods recognizedby those having skill in the art. Dispersion equipment can be operatedin batch, semi-batch, or continuous mode. Examples of mixers includerotor-stator, microfluidizer, high pressure homogenizer, ultrasonic,impinging jet, Cowles™ blade, planetary mixers, and melt kneadingdevices such as extruders.

A process for producing the dispersions in accordance with the presentinvention is not particularly limited.

In another embodiment, the aqueous dispersion can be formed in acontinuous high shear mixer. In this embodiment, the first streamcomprising one or more carbamate are supplied to a continuous high shearmixer from a suitable liquid pump for example, a syringe pump, gearpump, or progressive cavity pump. The first stream is flowed through afirst conduit and merged continuously with a second stream containing acontinuous aqueous phase that is flowed through a second conduit. Thefirst and second streams are merged into a disperser in the presence ofa stabilizing agent, e.g. surfactant, with an optional neutralizingagent. The agents can be added to either the first or second stream, oras a separate stream. A third stream comprising water can be addeddownstream from the disperser. The flow rates of the streams areadjusted to achieve a dispersion having the desired amount of polymerphase and percent solids. The disperser can be any one of a number ofcontinuous inline mixers, for example, an IKA high-shear mixer, Oakesrotor stator mixer, Ross mixer, Silverson mixer, or centrifugal pump.The rpm setting of the disperser can be used to help control theparticle size of the dispersed hydrophobic phase in the dispersion. Thesystem can be heated to provide the polymer and neutralizer componentsat a suitable viscosity for pumping. In some embodiments, the dispersionis further cooled after exiting the disperser by the use of a suitableheat exchanger.

In another embodiment, the aqueous dispersion can be formed in a batchor semi-batch high shear mixer.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, coating layers and adhesives made therefrom, andmethod of making such articles, in accordance with any of the precedingembodiments, except that the polycarbamate is prepared through freeradical emulsion or suspension addition polymerization product of one ormore α,β-ethylenically unsaturated monomers at least one of whichcomprises carbamate functionality. Alternatively, an polycarbamate canbe prepared through free radical polymerization in solvent of one ormore α,β-ethylenically unsaturated monomers at least one of whichcomprises carbamate functionality. The resulting polycarbamate can thenbe dispersed in water using shear.

Examples of suitable organic solvents are non-polar or polar organicsolvents such as, for example, an alkane (e.g., a (C₆-C₁₂)alkane), ether(e.g., (C₂-C₁₂)ether, e.g., a (C₂-C₁₂)dialkyl ether), carboxylic ester(e.g., a (C₂-C₁₂)carboxylic ester), ketone (e.g., a (C₃-C₁₂)ketone),secondary or tertiary carboxamide (e.g., a secondary or tertiary(C₃-C₁₂)carboxamide), sulfoxide (e.g., a (C₂-C₁₂)sulfoxide), or amixture of two or more thereof.

In an aspect of the present invention, the latex is an acrylic latexcontaining structural units of carbamate functional groups. Thecarbamate functional group can be incorporated using ethylenicallyunsaturated monomers containing carbamate groups. Examples of suchmonomers include: 2-Propenic acid, 2-[(aminocarbonyl)oxy]propyl ester;2-Propenic acid, 2-[(aminocarboxy)oxy]-1-methylethyl ester; 2-Propenicacid, 2-methyl-2-[(aminocarbonyl)oxy]ethyl ester; 2-Propenic acid,2-[(aminocarbonyl)oxy]propyl ester; or 2-Propenic acid,2-methyl-2-[(aminocarbonyl)oxy]-1-methylethyl ester.

The emulsion polymer typically includes at least one copolymerizednonionic ethylenically unsaturated monomer not bearing carbamatefunctionality such as, a (meth)acrylic ester monomer includingmethyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate,2-ethylhexyl(meth)acrylate, hydroxylethyl(meth)acrylate, andhydroxypropyl(meth)acrylate; ureido-functional(meth)acrylate;acrylonitrile, acrylamide styrene or substituted styrenes; vinyltoluene; butadiene; monoethylenically unsaturated acetophenone orbenzophenone derivatives such as, for example are taught in U.S. Pat.No. 5,162,415; vinyl acetate or other vinyl esters, vinyl monomers suchas vinyl chloride, vinylidene chloride, and N-vinyl pyrollidone. By“nonionic monomer” herein is meant that the copolymerized monomerresidue does not bear an ionic charge between pH 1 to 14. The use of theterm “(meth)” followed by another term such as (meth)acrylate, as usedthroughout the disclosure, refers to both acrylates and methacrylates.

The emulsion polymer may also include at least one copolymerizableethylenically unsaturated ionic monomer, most notably (meth)acrylicacid, crotonic acid, itaconic acid, fumaric acid, maleic acid,monomethyl itaconate, monobutyl fumarate, maleic anhydride,2-acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, styrenesulfonic acid, 1-allyloxy-2-hydroxypropane sulfonic acid, alkyl allylsulfosuccinic acid, sulfoethyl(meth)acrylate,phosphoalkyl(meth)acrylates such as phosphoethyl(meth)acrylates,phosphopropyl(meth)acrylates and phosphobutyl(meth)acrylates,phosphoalkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates,phosphodialkyl(meth)acrylates, phosphodialkyl crotonates, and allylphosphates. In one embodiment, the copolymerizable ethylenicicallyunsaturated monomer is selected from a group includingphosphoalkyl(meth)acrylates, such as phosphoethylmethacrylate, and2-acryl amido-2-methylpropane sulfonic acid.

Furthermore, the acrylic latexes may also include structural units ofother monomers capable of imparting co-curable functionality, such asglycidyl(meth)acrylates and acetoacetoxyethyl(meth)acrylates.

In certain embodiments it may be advantageous to incorporate into thepolymer copolymerized multi-ethylenically unsaturated monomer groups.Multi-ethylenically unsaturated monomers include, for example,allyl(meth)acrylate, diallyl phthalate, 1,4-butylene glycoldi(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, and divinyl benzene. It may be especially advantageousto incorporate such monomer groups non-uniformly into the polymer toform multiphase polymer particles to create a core-shell, hemispherical,or occluded morphology.

It may be advantageous to include chain transfer agents in the latexpreparation. Examples of chain transfer agents include, but are notlimited to, dodecylmercaptan, butylmercaptopropionate,methylmercaptopropionate, mercaptopropionic acid, etc.

In certain embodiments, it may be beneficial to use multiphase polymerparticles such as those disclosed by Duda et al. in Langmuir 2005, 21,1096-1102. The preparation of these morphologies is well known in theart. A multi-stage emulsion polymerization process usually results inthe formation of at least two mutually incompatible polymercompositions, thereby resulting in the formation of at least two phases.The mutual incompatibility of two or more polymer compositions and theresultant multiphase structure of the polymer particles may bedetermined in a variety of ways including scanning electron microscopyusing staining techniques to emphasize the difference between thephases.

Multiphase polymer particles may be of various geometries includingcore/shell or core/sheath particles, core/shell particles with shellphases incompletely encapsulating the core, and core/shell particleswith a multiplicity of cores. The final properties of these latexes areoften achieved by balancing the monomer compositions of the individualphases and their relative proportions. For the present invention, it maybe advantageous to use disparate or similar Tgs, and similar ordisparate hydrophobicities. The end use application of the latex usuallydictates the properties of each polymer phase.

The morphology of the host latex is not limited to strictly organicmaterials. It may be advantageous to make use of polymers that haveembedded or adsorbed inorganic phases or domain, for example,polymer-encapsulated opacifying pigment particles comprising i)opacifying pigment particles having a diameter in the range of 100 nm to500 nm and an index of refraction from 1.8 to 4.5; ii) an encapsulatingpolymer that contains polymerized units of a sulfur acid monomer, or asalt thereof, and iii) a polymeric dispersant for the encapsulatedopacifying pigment particles and the polymer, which dispersant containssulfur acid groups, or salts thereof, and amine groups, as described,for example, in U.S. Patent Publication US 2010/0298483 ALIn analternative embodiment, the instant invention provides a crosslinkablecomposition, a crosslinked composition, method of producing the same,coating layers and adhesives made therefrom, and method of making sucharticles, in accordance with any of the preceding embodiments, exceptthat the polyaldehyde has from 2 to 20 carbon atoms.

The aqueous dispersion comprises from 0.5 to 15 percent by weight of thepolyaldehyde component, based on the weight of the total dispersionsolids; for example, from 0.5 to 10 percent by weight of thepolyaldehyde component, based on the weight of the dispersion; or in thealternative, from 1 to 5 percent by weight of the polycarbamatecomponent, based on the weight of the total dispersion solids. As usedherein, the term “polyaldehyde” means a molecule containing two or morealdehyde groups or their hydrates, or their acetals or hemiacetals,wherein the molecule is capable of reacting with the polycarbamatecomponent. As used herein, the phrase “react together” means creatingone or more covalent bonds between two or more molecules, or portionsthereof.

The aldehyde group can be written herein as —C(═O)H or —CHO. Thepolyaldehyde component of the present invention may have two or morealdehyde groups. The polyaldehyde can be a cyclic, straight or branched;cyclic and nonaromatic; cyclic and aromatic (e.g.,3-formylbenzaldehyde), or a combination thereof.

In another embodiment, the polyaldehyde has from 2 to 20 carbon atoms.In another embodiment, the polyaldehyde has greater than 20 carbonatoms, with the proviso that a polyaldehyde having greater than 20carbon atoms has at least one aldehyde group for every 30 carbon atoms.

In one embodiment, the polyaldehyde is selected from the groupconsisting of (cis,trans)-1,4-cyclohexanedicarboxyaldehydes,(cis,trans)-1,3-cyclohexanedicarboxyaldehydes, glutaraldeyde, glyoxal,combinations thereof, and/or mixtures thereof. Exemplary polyaldedyes,e.g. glutaraldeyde, are commercially available under the trade nameUCARCIDE™ 42 available from The Dow Chemical Company. Other exemplarypolyaldedyes, e.g. glyoxal, are commercially available from BASF.

The polyaldehyde of the present invention is substantially formaldehydefree. As used herein, the term “substantially formaldehyde free” meansthat the multicomponent composition or ambient temperature curablecomposition comprises less than 500 ppm of free formaldehyde, based onthe total weight of polyaldehyde solids, preferably, less than 300 ppm,or, more preferably, less than 200 ppm. The compositions of the presentinvention contain so little of resins made from formaldehyde, such asaminoplasts and phenol or resole formaldehyde condensates, that theamount of free formaldehyde in such compositions meets the definition of“substantially formaldehyde free”.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, coating layers and adhesives made therefrom, andmethod of making such articles, in accordance with any of the precedingembodiments, except that the acid catalyst has a pKa of less than 6.0.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, coating layers and adhesives made therefrom, andmethod of making such articles, in accordance with any of the precedingembodiments, except that the acid catalyst has a pKa of less than 4.0

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, coating layers and adhesives made therefrom, andmethod of making such articles, in accordance with any of the precedingembodiments, except that the acid catalyst is Lewis acid.

Any compound, substance or material suitable for increasing a rate ofreaction of a carbamate group (—O—C(═O)—NH₂) with an aldehyde group(—C(═O)H) can be employed as the acid catalyst, i.e. triggering agent.Examples of acid catalyst, i.e. triggering agents are Lewis acids (e.g.,boron trifluoride etherate) and protic acids (i.e., Brønsted acids).Preferably, the acid catalyst, i.e. triggering agent comprises a proticacid characterizable as having a pK_(a) of 6 or lower, wherein pK_(a) isnegative base-10 logarithm of acid dissociation constant, K_(a), of theprotic acid. Thus, the ambient temperature curable composition of thepresent invention has a pH of 7.0, or less, preferably, from pH 3 topH<6. A preferred protic acid is an inorganic protic acid or organicprotic acid. A preferred inorganic protic acid is phosphoric acid orsulfuric acid. A preferred organic protic acid is carboxylic acid,phosphonic acid, or sulfonic acid. A preferred carboxylic acid is aceticacid, trifluoroacetic acid, propionic acid, or a dicarboxylic acid. Apreferred phosphonic acid is methylphosphonic acid. A preferred sulfonicacid is methanesulfonic acid, benzenesulfonic acid, a camphorsulfonicacid; para-toluenesulfonic acid, or dodecylbenzenesulfonic acid.Examples of suitable Lewis acid curing catalysts are AlCl₃;benzyltriethylammonium chloride (TEBAC); Cu(O₃SCF₃)₂; (CH₃)₂BrS⁺Br⁻;FeCl₃ (e.g., FeCl₃.6H₂O); HBF₄; BF₃.O(CH₂CH₃)₂; TiCl₄;SnCl₄; CrCl₂;NiCl₂; and Pd(OC(O)CH₃)₂.

The acid catalyst, i.e. triggering agent can be unsupported (no solidsupport) or supported, i.e. covalently bonded to a solid support.Examples of supported triggering agents are supported curing catalystssuch as supported acid catalysts such as acid (H⁺) forms of cationexchange-type polymer resins (e.g., ethanesulfonic acid,2-[1-[difluoro[(1,2,2-trifluoroethenyl)oxy]methyl]-1,2,2,2-tetrafluoroethoxy]-1,1,2,2-tetrafluoro-,polymer with 1,1,2,2-tetrafluoroethene sold under trade name NAFION NR50 (E. I. du Pont de Nemours & Co., Inc., Wilmington, Del.) andethenylbenzenesulfonic acid polymer with diethenylbenzene sold asAMBERLYST™ 15 (Rohm and Haas Co., subsidiary of The Dow ChemicalCompany, Midland, Mich., USA.).

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, in accordance with any of the preceding embodiments,except that the acid catalyst is a functional group which isincorporated into the backbone of the polycarbamate.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, coating layers and adhesives made therefrom, andmethod of making such articles, in accordance with any of the precedingembodiments, except that the composition further comprises a curinginhibitor. Curing inhibitors may include, for example, alcohols, water,or mixtures thereof. In one embodiment, the alcohol is present at aconcentration of from 0.5 wt % to 50 wt %, based on the total weight ofsolids in the composition, or more preferably, at most 20 wt %, and,still more preferably, at most 10 wt %. Preferably, water is present ata concentration of from 20% wt % to 70 wt %, based on the total weightof solids in the composition, or more preferably, from 30 wt % to 60 wt%.

In an alternative embodiment, the instant invention provides acrosslinkable composition, a crosslinked composition, method ofproducing the same, coating layers and adhesives made therefrom, andmethod of making such articles, in accordance with any of the precedingembodiments, except that the alcohol is selected from the groupconsisting of ethanol, 1-propanol, 1-butanol, 1-pentanol, Ethyleneglycol monoalkyl ethers, diethylene glycol monoalkyl ethers, propyleneglycol monoalkyl ethers and dipropylene glycol monoalkyl ethers,2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate, combinations thereof,and mixture thereof.

The crosslinkable aqueous composition of the invention may contain inaddition to water, a polycarbamate comprising at least an average of 2.0carbamate functional groups, a polyaldehyde comprising at least twoaldehyde groups, and an acid catalyst; additional film forming or nonfilm forming polymers, extenders, emulsifiers, coalescing agents,plasticizers, antifreezes, curing agents, buffers, neutralizers,thickeners, rheology modifiers, humectants, wetting agents, biocides,anti-foaming agents, UV absorbers, fluorescent brighteners, light orheat stabilizers, chelating agents, dispersants, tackifiers, colorants,waxes, water-repellants and pigments. Exemplary pigments include TiO₂,lamp black, talc, calcium carbonate, or clay.

Preferably in the present invention, the curing temperature of theambient temperature curable composition is 80° C. or lower, morepreferably 60° C. or lower, still more preferably 40° C. or lower, andeven more preferably 30° C. or lower. A preferred minimum effectivecuring temperature is a minimum temperature effective for curing theinvention ambient temperature curable composition to yield the inventioncrosslinked composition within 7 days. The curing step of the inventionprocess employing the invention ambient temperature curable compositionremarkably can be performed at ambient temperature (i.e., 60° C. orlower). In some embodiments the ambient temperature for curing is atleast 0° C., in some embodiments at least 10° C., and in someembodiments at least 20° C. In some embodiments the ambient temperaturefor curing is 50° C. or less, in some embodiments 40° C. or less, insome embodiments 35° C. or less, and in some embodiments 30° C. or less.A preferred ambient temperature for curing is from 19° C. to 29° C.

Preferably a crosslinked composition prepared according to the presentinvention forms a coating or adhesive that exhibits good to excellentcross-hatch adhesion, water resistance, chemical resistance, resistanceto rubbing with methyl ethyl ketone, high pendulum hardness, or acombination of any two or more thereof.

The crosslinked coating compositions of the present invention, eventhose produced by curing at room temperature, have a high degree ofcrosslinking. This high degree of crosslinking preferably is evidencedby a spectral property (e.g., obtained from proton-nuclear magneticresonance (¹H-NMR) spectroscopy, ¹³C-NMR spectroscopy, or FT-IRspectroscopy) or, more preferably, by one or more improved performanceproperties. Preferably at least one of the improved performanceproperties is cross-hatch adhesion, water resistance, deteriorationresistance to methyl ethyl ketone rubs, or high pendulum hardness.

Preferably, methods of using the crosslinked compositions of the presentinvention comprise coatings formed with the crosslinkable coatingcompositions, wherein the coating exhibits a water resistance,resistance to rubbing with methyl ethyl ketone, high pendulum hardness,cross-hatch adhesion, or a combination of any two or more thereof.

An adhesive composition of the present invention may comprise theinvention crosslinked coating compositions, which is disposed betweenand in independent operative contact with at least a portion of each oftwo substrates capable of being adhered to each other.

The coating composition of the present invention comprises a layer ofthe invention crosslinked coating compositions, which is in coatingoperative contact to at least a portion of a substrate capable of beingcoated.

The crosslinked composition of the present invention may comprise asealant, which is disposed in sealing operative contact to a substratecapable of being sealed. Preferably the invention sealant prevents orinhibits passage of a liquid or gas, dust or smoke; more preferably aliquid or gas; still more preferably a liquid, and even more preferablywater. In some embodiments the sealant further comprises an inert fillermaterial (e.g., inert finely-divided powder). In methods of using thesealants of the present invention, sealed substrates can be prepared byany suitable method. For example, a method of sealing a substratecomprises contacting the invention ambient temperature curablecomposition to at least a portion of the substrate to yield a compositematerial comprising a curable coating of the ambient temperature curablecomposition in operative contact with at least the portion of thesubstrate; and curing the curable coating of the ambient temperaturecurable composition of the composite material at a curing temperature offrom 0° C. to less than 80° C. so as to prepare a sealed substratecomprising a sealant layer of the invention crosslinked composition insealing operative contact to at least the portion of the substrate. Forexample, the curable composition may be cured at a curing temperature of30° C. or less.

The invention coated substrate can be prepared by any suitable method.For example, in a method of coating a surface of a substrate, the methodcomprises applying invention ambient temperature curable composition toat least a portion of the surface of the substrate and curing thecurable coating of the ambient temperature curable composition of thecomposite material at a curing temperature of 80° C. or less, or, forexample, 30° C. or less, so as to prepare a coated substrate comprisinga crosslinked polyurethane.

The invention ambient temperature curable composition can be applied tothe surface of the substrate(s) by any suitable applying means such as,for example, brushing, calendaring, rolling, spraying, mopping,troweling, or dipping. The substrate being coated, adhered to, or sealedcan be of any shape including, for example, a flat or rolled sheet(e.g., cylinder), sphere, beads, finely divided particles, and the like.The surface of the substrate being coated, adhered to, or sealed can beirregular or regular, continuous or discontinuous, porous or non-porous,jointed or not jointed.

The substrates suitable for being adhered to, coated, or sealedindependently can comprise any material. Examples of suitable materialare wood, metal, ceramic, plastic, concrete, asphalt, hair, paper,leather, rubber, glass, foam and/or textiles.

EXAMPLES

The following examples illustrate the present invention but are notintended to limit the scope of the invention.

Formulation components:

Butyl acrylate BA 2-Ethylhexyl acrylate EHA Methyl methacrylate MMAMethyl ethyl ketone MEK Isopropyl alcohol IPA PhosphoethylmethacrylatePEM Hydroxypropyl carbamate acrylate, 70% in Ethanol HPCAn-Dodecylmercaptan nDDM t-Butylhydroperoxide, 70% tBHP Isoascorbic AcidIAA Sodium persulfate, 99% NaPS Ammonium persulfate, 99% APSAlkylpolyethoxysulfate, Na salt (31%) Surfactant A2-acrylamide-2-methylpropane sulfonic acid AMPSEthyelendiaminetetraacetic acid EDTA

Polycarbamate Component 1

Polycarbamate component 1 is an emulsion polymer (MMA/BA/HPCA Latex)prepared according to the following process.

A monomer emulsion was prepared by mixing deionized water (155 g),Surfactant A (24.3 g), BA (321.6 g), MMA (382.4 g), HPCA (114.3 g), AMPS(16 g), and n-DDM (6 g) in a first vessel. A reactor flask was chargedwith deionized water (675 g) and Surfactant A (5 g), and then thetemperature of the mixture was increased to approximately 82° C. under aN₂ purge. The reactor flask was charged with a 35.6 g of the monomeremulsion followed by a 30 g of deionized water rinse. A solution of NaPS(3.2 g) in deionized water (40 g) was added to the reactor flaskfollowed by a deionized water rinse (20 g). After a peak exotherm, themonomer emulsion was fed to the reactor flask at a rate of 7.5 g/min for10 minutes, and then increased to 15.2 g/min for an additional 60 min,while maintaining a reactor flask temperature of approximately 80° C.Subsequently, the monomer emulsion line was rinsed with deionized water(45 g) and the reactor flask was maintained at approximately 80° C. for10 minutes before being cooled to 65° C. At 65° C., a solutioncontaining 0.15 weight percent aqueous iron sulfate heptahydrate (3.5 g)and 1.0 weight percent aqueous solution of EDTA (0.5 g) was addedfollowed by the addition of separate solutions of t-BHP (0.40 g in 10 gof deionized water) and IAA (0.15 g in 10 g of deionized water). Thereactor flask was maintained at approximately 65° C. for 15 minutesbefore separate solutions of t-BHP (0.40 g in 10 g of deionized water)and IAA (0.15 g in 10 g of deionized water) were added to the reactorflask. After 15 minutes at 65° C., the content of the reactor was cooledto 30° C. The emulsion polymer (polycarbamate component 1) was filteredvia 100 mesh screen, and characterized for its solids, pH, and particlesize. The results are reported in Table 1.

TABLE 1 Polycarbamate component 1 DI water (g) 155 Surfactant A (g) 24.3BA (g) 321.6 MMA (g) 382.4 HPCA (g) 114.3 n-DDM (g) 6 AMPS (g) 16Particle size (nm) 123 Latex solids (%) 43.1 pH 1.3

Polycarbamate Component 2

Polycarbamate component 2 is an emulsion polymer (MMA/Sty/HPCA/2-EHALatex) prepared according to the following process.

A monomer emulsion was prepared by mixing deionized water (428 g),Surfactant A (39.9 g), STY, (316 g), PEM (50.4 g), MMA (396.8 g), HPCA(225.6 g) and 2-EHA (646.4 g) in a first vessel. A reactor flask wascharged with deionized water (708 g) and Surfactant A (2.2 g), and thenthe temperature of the mixture was increased to approximately 82° C.under a N₂ purge. The reactor flask was charged with a 61.4 g of themonomer emulsion followed by a deionized water rinse (20 g). n-DDM (7.8g) and deionized water (10 g) was then added to the monomer emulsion.The reaction flask was then charged with a solution of APS (5.8 g in19.8 g of deionized water). After a peak exotherm, the monomer emulsionwas fed to the reactor at a rate of 6.9 g/minutes for 10 minutes, andthen increased to 14.2 g/minutes for an additional 140 minutes,maintaining a reactor temperature of approximately 80 to 81° C. Asolution of APS (3.1 g) in deionized water (87.8 g) was added to thereactor flask concurrently with the monomer emulsion feed at a rate of0.30 g/minutes for the first 20 minutes, and then increased to a rate of0.62 g/minutes for an additional 140 minutes. Deionized water (390 g)was co-fed to reactor for approximately 140 minutes. Subsequently, themonomer emulsion line was rinsed with deionized water (50 g) and thereactor flask was maintained at approximately 80 to 81° C. for 30minutes before being cooled to 65° C. At 65° C., a solution containing0.15 weight percent aqueous iron sulfate heptahydrate (13.8 g) and 1.0weight percent aqueous solution of EDTA (2.1 g) was added followed byseparate solutions of t-BHP (1.5 g in 18.6 g of deionized water) and IAA(0.7 g in 19 g of deionized water) were co-fed separately over 30minutes. MMA (3.0 g) is added to the reactor flask followed by theaddition of deionized water (3.3 g) 10 minutes after co-feeds werecompleted. Immediately thereafter, separate solutions of t-BHP (0.8 g in6.6 g of deionized water) and IAA (0.6 g in 16.8 g of deionized water)were added to the reactor flask. The reactor was then cooled to 30° C.The emulsion polymer, polycarbamate component 2, was filtered via 100mesh screen and characterized for its solids, pH, and particle size. Theresults are reported in Table 2.

TABLE 2 Polycarbamate component 2 DI water (g) 428 Surfactant A (g) 39.9Sty (g) 316 PEM (g) 50.4 MMA (g) 396.8 HPCA (g) 225.6 2-EHA 646.4 n-DDM7.8 ME seed (g) 61.4 H₂O cofeed (g) 390 Particle size (nm) 142 Latexsolids (%) 44.8 pH 1.3

Polycarbamate Component 3

Polycarbamate component 3 is an emulsion polymer (MMA/Sty/HPCA/2-EHALatex) prepared according to the following process.

A monomer emulsion was prepared by mixing deionized water (428 g),Surfactant A (39.9 g), STY, (316 g), PEM (50.4 g), MMA (565.6 g), HPCA(225.6 g) and 2-EHA (477.8 g) in a first vessel. A reactor flask wascharged with deionized water (708 g) and Surfactant A (2.2 g), and thenthe temperature of the mixture was increased to approximately 82° C.under a N₂ purge. The reactor flask was charged with a 61.4 g of themonomer emulsion followed by a deionized water rinse (20 g). n-DDM (7.8g) and deionized water (10 g) was then added to the monomer emulsion.The reaction flask was then charged with a solution of APS (5.8 g in19.8 g of deionized water). After a peak exotherm, the monomer emulsionwas fed to the reactor at a rate of 6.9 g/minutes for 10 minutes, andthen increased to 14.2 g/minutes for an additional 140 minutes,maintaining a reactor temperature of approximately 80 to 81° C. Asolution of APS (3.1 g) in deionized water (87.8 g) was added to thereactor flask concurrently with the monomer emulsion feed at a rate of0.30 g/minutes for the first 20 minutes, and then increased to a rate of0.62 g/minutes for an additional 140 minutes. Deionized water (390 g)was co-fed to reactor for approximately 140 minutes. Subsequently, themonomer emulsion line was rinsed with deionized water (50 g) and thereactor flask was maintained at approximately 80 to 81° C. for 30minutes before being cooled to 65° C. At 65° C., a solution containing0.15 weight percent aqueous iron sulfate heptahydrate (13.8 g) and 1.0weight percent aqueous solution of EDTA (2.1 g) was added followed byseparate solutions of t-BHP (1.5 g in 18.6 g of deionized water) and IAA(0.7 g in 19 g of deionized water) were co-fed separately over 30minutes. MMA (3.0 g) is added to the reactor flask followed by theaddition of deionized water (3.3 g) 10 min after co-feeds werecompleted. Immediately thereafter, separate solutions of t-BHP (0.8 g in6.6 g of deionized water) and IAA (0.6 g in 16.8 g of deionized water)were added to the reactor flask. The reactor was then cooled to 30° C.The emulsion polymer, polycarbamate component 3, was filtered via 100mesh screen and characterized for its solids, pH, and particle size. Theresults are reported in Table 3.

TABLE 3 Polycarbamate component 3 DI water (g) 428 Surfactant A (g) 39.9Sty (g) 316 PEM (g) 50.4 MMA (g) 565.6 HPCA (g) 225.6 2-EHA 477.8 n-DDM7.8 ME seed (g) 61.4 H₂O cofeed (g) 390 Particle size (nm) 137 Latexsolids (%) 44.9 pH 1.3

Polycarbamate Component 4

Polycarbamate component 4 is a solvent diluted acrylic polymer made fromthe reaction of a commercial acrylic polyol, PARALOID™ AU-608×,commercially available from The Dow Chemical Company, with methylcarbamate and diluted with xylene.

Into a reactor system comprising a 3 necked 2000 mL round bottom flaskequipped with a mechanical stirrer, Dean-Stark trap, condenser, andnitrogen bubbler system was place PARALOID™ AU-608× acrylic polyol (1500g, 1.334 moles hydroxyl), methyl carbamate (100.2 g, 1.334 mole) anddibutyltin oxide catalyst (4.8 g, 0.30%). The system was flushed withnitrogen gas, the reaction contents were heated to lower the viscosity,and stirring was initiated. Once the methyl carbamate dissolved, theresulting reaction mixture was slowly heated to 140° C. and held at thistemperature. The methanol produced was collected and the volume of thisbyproduct was recorded. Once the methanol was no longer beingsignificantly generated, nitrogen was flushed over the liquid contentsto drive the remaining methanol and excess methyl carbamate from thereaction mixture. For a typical reaction cycle, the heating at 140° C.was performed for 8 hours on a first day, the heating was stopped (heatsource is turned off), and then on a second day the heating at 140° C.was continued for another 8 hours with nitrogen gas passing over thereaction mixture. Carbon-13 nuclear magnetic resonance (¹³C-NMR) inperdeuterated dimethyl sulfoxide (d6-DMSO) analysis shows that themethyl carbamate was removed by observation of the methyl carbonresonance. During the removal of methanol and unreacted methylcarbamate, if the viscosity of the resulting mixture was too high suchthat the product would be slow to pour, then mixed xylenes were added tothe reaction mixture to lower the viscosity so that the product wassatisfactorily pourable. A hydroxyl number titration showed 9 mg KOH/gand acid titration indicated 4.5 mg KOH/g which validated conversion ofhydroxyl groups to carbamate groups. On completion, thepolyacrylic-based polycarbamate of polycarbamate component 4 was a clearliquid solution. A TGA analysis showed a weight percent solids of 62 wt.%. The carbamate content of the polyacrylic-based polycarbamate wasdetermined by subtracting the hydroxyl content thereof polycarbamatecomponent 4 from the hydroxyl content of the starting PARALOID™ AU-608Xacrylic polyol. The equivalent weight was calculated as Ew=1431.3 geq/mol (@62% solids).

CHDA (Aldehyde component) is approximately a 1:1 1,3cyclohexanedicarboxaldehyde and 1,4-cyclohexanedicarboxaldehyde, havinga weight average molecular weight (M_(w)) of 140.1 g/mol, and anequivalent weight (EW) of 70.05 equi g/mol.

Acid Catalyst 1 comprises: 25% p-toluenesulfonic acid (PTSA) solution; 1g PTSA; and 3 g MEK (methyl ethyl ketone).

Steel Substrate comprised a steel metal sheet (Act Test Panels) havingthe following dimensions: Cold Roll Steel 4 in.×12 in.×0.032 in. andpolished and clean.

The coating compositions were applied to the steel substrate using adoctor blade having a gap of 5 mil.

Wood Substrate comprised a Poplar board ¼ in.×4 in.×48 in. (purchasedfrom Home Depot) that was cut down 5 in. lengths (5 in.×4 in.×¼ in.).They were coated three times with the formulation by using a foam brush.After each coat, the coating was allowed to dry for 1 day and thenlightly sanded before the addition of the next coat. The last coat, thethird coat, was not sanded.

Comparative Emulsion Polymer 1

Comparative emulsion polymer 1 is (MMA/Sty/2-EHA Latex) preparedaccording to the following process.

A monomer emulsion was prepared by mixing deionized water (408 g),Surfactant A (39.9 g), STY, (294.4 g), PEM (47.2 g), MMA (476 g), and2-EHA (639 g) in a first vessel. A reactor flask was charged withdeionized water (708 g) and Surfactant A (2.2 g), and then thetemperature of the mixture was increased to approximately 82° C. under aN₂ purge. The reactor flask was charged with a 59.5 g of the monomeremulsion followed by a deionized water rinse (20 g). n-DDM (7.4 g) anddeionized water (10 g) was then added to the monomer emulsion. Thereaction flask was then charged with a solution of APS (5.8 g in 19.8 gof deionized water). After a peak exotherm, the monomer emulsion was fedto the reactor at a rate of 6.9 g/minutes for 10 minutes, and thenincreased to 14.2 g/minutes for an additional 140 minutes, maintaining areactor temperature of approximately 80 to 81° C. A solution of APS (3.1g) in deionized water (87.8 g) was added to the reactor flaskconcurrently with the monomer emulsion feed at a rate of 0.30 g/minutesfor the first 20 minutes, and then increased to a rate of 0.62 g/minutesfor an additional 140 minutes. Deionized water (390 g) was co-fed toreactor for approximately 140 minutes. Subsequently, the monomeremulsion line was rinsed with deionized water (50 g) and the reactorflask was maintained at approximately 80 to 81° C. for 30 minutes beforebeing cooled to 65° C. At 65° C., a solution containing 0.15 weightpercent aqueous iron sulfate heptahydrate (13.8 g) and 1.0 weightpercent aqueous solution of EDTA (2.1 g) was added followed by separatesolutions of t-BHP (1.5 g in 18.6 g of deionized water) and IAA (0.7 gin 19 g of deionized water) were co-fed separately over 30 minutes. MMA(3.0 g) is added to the reactor flask followed by the addition ofdeionized water (3.3 g) 10 min after co-feeds were completed.Immediately thereafter, separate solutions of t-BHP (0.8 g in 6.6 g ofdeionized water) and IAA (0.6 g in 16.8 g of deionized water) were addedto the reactor flask. The reactor was then cooled to 30° C. The emulsionpolymer, comparative emulsion polymer 1, was filtered via 100 meshscreen and characterized for its solids, pH, and particle size. Theresults are reported in Table 4.

TABLE 4 Comparative Emulsion Polymer 1 DI water (g) 408 Surfactant A (g)39.9 Sty (g) 294.4 PEM (g) 47.2 MMA (g) 476 HPCA (g) 0 2-EHA 639 n-DDM7.4 ME seed (g) 59.5 H₂O cofeed (g) 490 Particle size (nm) 119 Latexsolids (%) 45.4 pH 1.3

Comparative Emulsion Polymer 2

Comparative emulsion polymer 2 is (MMA/Sty/2-EHA Latex) preparedaccording to the following process.

A monomer emulsion was prepared by mixing deionized water (408 g),Surfactant A (39.9 g), STY, (294.4 g), PEM (47.2 g), MMA (639 g), and2-EHA (476 g) in a first vessel. A reactor flask was charged withdeionized water (708 g) and Surfactant A (2.2 g), and then thetemperature of the mixture was increased to approximately 82° C. under aN₂ purge. The reactor flask was charged with a 59.5 g of the monomeremulsion followed by a deionized water rinse (20 g). n-DDM (7.4 g) anddeionized water (10 g) was then added to the monomer emulsion. Thereaction flask was then charged with a solution of APS (5.8 g in 19.8 gof deionized water). After a peak exotherm, the monomer emulsion was fedto the reactor at a rate of 6.9 g/minutes for 10 minutes, and thenincreased to 14.2 g/minutes for an additional 140 minutes, maintaining areactor temperature of approximately 80 to 81° C. A solution of APS (3.1g) in deionized water (87.8 g) was added to the reactor flaskconcurrently with the monomer emulsion feed at a rate of 0.30 g/minutesfor the first 20 minutes, and then increased to a rate of 0.62 g/minutesfor an additional 140 minutes. Deionized water (390 g) was co-fed toreactor for approximately 140 minutes. Subsequently, the monomeremulsion line was rinsed with deionized water (50 g) and the reactorflask was maintained at approximately 80 to 81° C. for 30 minutes beforebeing cooled to 65° C. At 65° C., a solution containing 0.15 weightpercent aqueous iron sulfate heptahydrate (13.8 g) and 1.0 weightpercent aqueous solution of EDTA (2.1 g) was added followed by separatesolutions of t-BHP (1.5 g in 18.6 g of deionized water) and IAA (0.7 gin 19 g of deionized water) were co-fed separately over 30 minutes. MMA(3.0 g) is added to the reactor flask followed by the addition ofdeionized water (3.3 g) 10 minutes after co-feeds were complete.Immediately thereafter, separate solutions of t-BHP (0.8 g in 6.6 g ofdeionized water) and IAA (0.6 g in 16.8 g of deionized water) were addedto the reactor flask. The reactor was then cooled to 30° C. The emulsionpolymer, comparative emulsion polymer 2, was filtered via 100 meshscreen and characterized for its solids, pH, and particle size. Theresults are reported in Table 5.

TABLE 5 Comparative Emulsion Polymer 2 DI water (g) 408 Surfactant A (g)39.9 Sty (g) 294.4 PEM (g) 47.2 MMA (g) 639.0 HPCA (g) 0 2-EHA 476 n-DDM7.4 ME seed (g) 59.2 H₂O cofeed (g) 490 Particle size (nm) 121 Latexsolids (%) 45.7 pH 1.3

Process for Preparing Inventive Formulations 1-2 and ComparativeFormulations A-B:

All formulations were made by adding ingredients dropwise to the binder,i.e. emulsion polymer, while stirring with an overhead mixer. Surfactantwas added first, if applicable. Neutralizer was added second, ifapplicable. If CHDA was added to the formulation, it was first mixedwith a coalescent agent, and the CHDA/coalescent mixture was added next.If glutaraldehyde was added, the coalescent agent was added first,followed by the aldehyde. A wetting agent, i.e. Byk 346, was added next,if applicable. Rheology modifier was added last, if applicable. Thisprocess was generally done over two to ten minutes depending on thenumber of ingredients added. All formulations were allowed to sit for anhour before being used to make coatings.

Inventive Formulation 1

Inventive formulation 1 was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 6. 0.87 grams of CHDA was dissolved in 2.16 grams ofProglyde DMM to form a premix. This premix was added dropwise to 50grams of polycarbamate component 1 while stirring with an overheadmixer, followed by the dropwise addition of 0.20 grams of Byk 346.

Inventive Formulation 2

Inventive formulation 2 was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 6.

2.16 grams of Proglyde DMM was added dropwise to 50 grams ofpolycarbamate component 1 while stirring with an overhead mixer,followed by the dropwise addition of 1.25 g of 50% glutaraldehyde, andthen followed by the dropwise addition 0.20 grams of Byk 346.

Comparative Formulation A

Comparative formulation A was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 6.

2.16 grams of Proglyde DMM was added dropwise to 50 grams ofpolycarbamate component 1 while stirring with an overhead mixer,followed by the dropwise addition 0.20 grams of Byk 346.

Comparative Formulation B

Comparative formulation B was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 6.

2.4 grams of a 10% solution of dimethylaminoethanol (DMAE) in water wasadded dropwise to 50 grams of polycarbamate component 1 while stirringwith an overhead mixer. 0.87 grams of CHDA ws dissolved in 2.16 grams ofProglyde DMM to form a premix. This premix was added dropwise to theneutralized polycarbamate component 1 while stirring with an overheadmixer, followed by the dropwise addition of 0.20 grams of Byk 346.

TABLE 6 Inventive Inventive Comparative Comparative FormulationFormulation Formulation Formulation 1 2 A B Polycarbamate 50 50 50 50Component 1 Triton X-405 0 0 0 0 10% DMAE 0 0 0 2.4 DMM 2.16 2.16 2.162.16 CHDA 0.87 0 0 0.87 Glutaraldehyde, 0 1.25 0 0 50% in water Byk 3460.20 0.20 0.20 0.20 Final 1.3 1.3 1.3 7.0 Formulation pHEvaluation of Coatings Derived from Inventive Formulations 1-2 andComparative Formulations A-B

Films of approximately 1 mil dry film thickness were made from InventiveFormulations 1-2 and Comparative Formulations A and B approximately fourhours after the formulations were made. Inventive Formulation 1 wassubsequently aged for three weeks at room temperature, and oneadditional week at 60° C. and then was used to make a new 1 mil thickdry film. The films were dried under ambient conditions (25° C.) for twoweeks before evaluating properties. Koenig (pendulum) hardness wasmeasured according to ASTM D-4366 using a TQC SP0500 Pendulum HardnessTester, and was reported in seconds in Table 7. Chemical resistancetests were done by placing a 23 mm diameter Whatman filter paper on thecoating and saturating it with the chemical, reported in Table 7. Thechemical was covered to prevent evaporation for one hour. The chemicaland filter paper were removed from the coating by hand and with a mildwater rinse. Chemical resistance was ranked 1-5 with 5 representing novisible sign of damage and no noticeable softening of the film, and 1representing complete dissolution of the coating by the chemical.Chemical resistance was tested for acetone, isopropyl alcohol and a50/50 mix of ethanol and water.

TABLE 7 Konig 50% Isopropyl Hardness Ethanol Alcohol Acetone Film From(s) Resistance Resistance Resistance Inventive 50.4 4 5 5 Formulation 1Inventive 37.8 3 5 5 Formulation 2 Comparative 29.6 2 1 1 Formulation AComparative 31.1 2 1 1 Formulation B Inventive 51.8 4 5 5 Formulation 1After Aging

Inventive Formulation 3

Inventive formulation 3 was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 8. 1.21 grams of CHDA was dissolved in 3.0 grams ofProglyde DMM to form a premix. 0.75 grams of Triton X-405 was addeddropwise to 67.0 grams of polycarbamate component 2 while stirring withan overhead mixer, followed by the dropwise addition of CHDA/ProglydeDMM premix, followed by the dropwise addition of 0.20 grams of Byk 346.

Comparative Formulation C

Comparative formulation C was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 8. 0.75 grams of Triton X-405 was added dropwise to67.0 grams of polycarbamate component 2 while stirring with an overheadmixer, followed by the dropwise addition of 3.0 grams of Proglyde DMM,followed by the dropwise addition of 0.20 grams of Byk 346.

Comparative Formulation D

Comparative formulation D was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 8. 1.35 grams of CHDA were dissolved in 3.0 grams ofProglyde DMM to form a premix. 0.75 grams of Triton X-405 was addeddropwise to 66.1 grams of Comparative Emulsion Polymer 1 while stirringwith an overhead mixer, followed by the dropwise addition ofCHDA/Proglyde DMM premix, followed by the dropwise addition of 0.20grams of Byk 346.

Comparative Formulation E

Comparative formulation E was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 8. 0.75 grams of Triton X-405 was added dropwise to66.1 grams of Comparative Emulsion Polymer 1 while stirring with anoverhead mixer, followed by the dropwise addition of 3.0 grams ofProglyde DMM, followed by the dropwise addition of 0.20 grams of Byk346.

TABLE 8 Inventive Comparative Comparative Comparative Formu- FormulationFormulation Formulation lation 3 C D E Polycarbamate 67.0 67.0 0 0Component 2 Comparative 0 0 66.1 66.1 Emulsion Polymer 1 Triton X-4050.75 0.75 0.75 0.75 DMM 3.0 3.0 3.0 3.0 CHDA 1.21 0 1.35 0 Byk 346 0.200.20 0.20 0.20 Final 1.3 1.3 1.3 1.3 Formulation pH

Evaluation of Coatings Derived from Inventive Formulation 3 andComparative Formulations C-E

Films of approximately 1 mil dry film thickness were made from InventiveFormulation 3 and Comparative Formulations C-E approximately four hoursafter the formulations were made. Inventive Formulation 3 wassubsequently aged for three weeks at room temperature, and oneadditional week at 60° C. and then was used to make a new 1 mil thickdry film. The films were dried under ambient conditions (25° C.) for twoweeks before evaluating properties. Koenig (pendulum) hardness wasmeasured according to ASTM D-4366 using a TQC SP0500 Pendulum HardnessTester, and was reported in seconds in Table 9. Chemical resistancetests were done by placing a 23 mm diameter Whatman filter paper on thecoating and saturating it with the chemical, reported in Table 9. Thechemical was covered to prevent evaporation for one hour. The chemicaland filter paper were removed from the coating by hand and with a mildwater rinse. Chemical resistance was ranked 1-5 with 5 representing novisible sign of damage and no noticeable softening of the film, and 1representing complete dissolution of the coating by the chemical.Chemical resistance was tested for acetone, isopropyl alcohol, a 50/50mix of ethanol and water, and MEK.

TABLE 9 Inventive Comparative Comparative Comparative Film Made Formu-Formulation Formulation Formulation From lation 3 C D E Konig 24.9 13.111.7 14.6 Hardness Acetone 5 3 3 3 Resistance MEK 5 3 3 3 Resistance IPA3 3 2 2 Resistance 50% Ethanol 2 2 2 3 Resistance

Inventive Formulation 4

Inventive formulation 4 was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 10. 1.21 grams of CHDA was dissolved in 4.5 grams ofProglyde DMM to form a premix. 0.75 grams of Triton X-405 was addeddropwise to 66.8 grams of polycarbamate component 3 while stirring withan overhead mixer, followed by the dropwise addition of CHDA/ProglydeDMM premix, followed by the dropwise addition of 0.20 grams of Byk 346.

Comparative Formulation F

Comparative Formulation F was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 10. 0.75 grams of Triton X-405 was added dropwise to66.8 grams of polycarbamate component 3 while stirring with an overheadmixer, followed by the dropwise addition of 4.5 grams of Proglyde DMM,followed by the dropwise addition of 0.20 grams of Byk 346.

Comparative Formulation G

Comparative Formulation G was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 10. 1.34 grams of CHDA was dissolved in 4.5 grams ofProglyde DMM to form a premix. 0.75 grams of Triton X-405 was addeddropwise to 65.7 grams of Comparative Emulsion Polymer 2 while stirringwith an overhead mixer, followed by the dropwise addition ofCHDA/Proglyde DMM premix, followed by the dropwise addition of 0.20grams of Byk 346.

Comparative Formulation H

Comparative Formulation H was prepared according to the above process,which is further defined below, based on the formulation componentsreported in Table 10. 0.75 grams of Triton X-405 was added dropwise to65.7 grams of Comparative Emulsion Polymer 2 while stirring with anoverhead mixer, followed by the dropwise addition of 4.5 grams ofProglyde DMM, followed by the dropwise addition of 0.20 grams of Byk346.

TABLE 10 Inventive Comparative Comparative Comparative Formu-Formulation Formulation Formulation lation 4 F G H Polycarbamate 66.866.8 0 0 Component 3 Comparative 0 0 65.7 65.7 Emulsion Polymer 2 TritonX-405 0.75 0.75 0.75 0.75 DMM 4.5 4.5 4.5 4.5 CHDA 1.21 0 1.34 0 Byk 3460.2 0.2 0.2 0.2 Final 1.3 1.3 1.3 1.3 Formulation pH

Evaluation of Coatings Derived from Inventive Formulation 4 andComparative Formulations F-H

Films of approximately 1 mil dry film thickness were made from InventiveFormulation 4 and Comparative Formulations F—H approximately four hoursafter the formulations were made. Inventive Formulation 4 wassubsequently aged for three weeks at room temperature, and oneadditional week at 60° C. and then was used to make a new 1 mil thickdry film. The films were dried under ambient conditions (25° C.) for twoweeks before evaluating properties. Koenig (pendulum) hardness wasmeasured according to ASTM D-4366 using a TQC SP0500 Pendulum HardnessTester, and was reported in seconds in Table 11. Chemical resistancetests were done by placing a 23 mm diameter Whatman filter paper on thecoating and saturating it with the chemical, reported in Table 1. Thechemical was covered to prevent evaporation for one hour. The chemicaland filter paper were removed from the coating by hand and with a mildwater rinse. Chemical resistance was ranked 1-5 with 5 representing novisible sign of damage and no noticeable softening of the film, and 1representing complete dissolution of the coating by the chemical.Chemical resistance was tested for acetone, isopropyl alcohol, a 50/50mix of ethanol and water, and MEK.

TABLE 11 Inventive Comparative Comparative Comparative Film MadeFormulation Formulation Formulation Formulation From 4 F G H Konig 87.783.3 69.5 89.3 Hardness Acetone 5 2 3 3 Resistance MEK 5 3 3 3Resistance IPA 5 3 2 2 Resistance 50% Ethanol 2 2 4 2 Resistance

Dispersion Polymer 1

Dispersion Polymer 1 is Polycarbamate Component 4 in water and dispersedas small particles in the water continues phase according to thefollowing process.

AU 608 Carbamate functional resin (solution in Xylene with 62% Nonvolatile matter) 100 g was heated to 35-40° C. and mixed with 5 g ofHitenol BC-10 (100% active, a polymerizable anionic surfactant obtainedfrom Montello Inc) in a polyethylene beaker. The content of the beakerwas stirred with a cowles type mechanical stirrer at an rpm of˜3500-4000 cpm for ˜1 minute to obtain uniform mixing. To this mixture,warm water (water at ˜35-40° C.) was added approximately at the rate of3 ml/minute while maintaining the stirring. As the water additionprogressed the viscosity of the mixture increased significantly andeventually, was a thick paste/gel after ˜20 ml of water addition. Wateraddition was suspended for 1-2 minutes while maintaining the stirring toensure uniform mixing of the high viscous (high internal phase emulsion)mixture. The water addition rate was increased to ˜10 ml/minute for nextstage (dilution stage) to obtain dispersion with final water content to50 g. The volume average particle size of the dispersion was measuredusing a Coulter LS 230 instrument and was shown to measure 2.4 micron. ATGA analysis indicated that Comparative Dispersion Polymer 1 measured apercent solids of 39.7% which resulted in a carbamate polymer equivalentweight for the dispersion as Ew=2233.03 g eq/mole (@39.7% solids).

Inventive Formulation 5

Inventive Formulation 5 comprises (a) 10.0 g of Dispersion Polymer 1;(b) 0.314 g of CHDA; (c) 0.171 g Acid Catalyst 1; and (d) 1 g of NMP(N-methyl-2-pyrolidone). Components a, b and d were placed in a flask,and mixed using a speed mixer to form a clear solution, and subsequentlycomponent c was added, and mixed via the speed mixer at approximately 22deg. C. for approximately one minute.

Inventive Formulation 6

Inventive Formulation 6 comprises (a) 10.0 g of Dispersion Polymer 1;(b) 0.314 g of CHDA; (c) 0.858 g Acid Catalyst 1; and (d) 1 g of NMP(N-methyl-2-pyrolidone). Components a, b and d were placed in a flask,and mixed using a speed mixer to form a clear solution, and subsequentlycomponent c was added, and mixed via the speed mixer at approximately 22deg. C. for approximately one minute.

Inventive Formulation 7

Inventive Formulation 7 comprises (a) 10.0 g of Dispersion Polymer 1;(b) 0.628 g of CHDA; (c) 0.184 g Acid Catalyst 1; and (d) 1 g of NMP(N-methyl-2-pyrolidone). Components a, b and d were placed in a flask,and mixed using a speed mixer to form a clear solution, and subsequentlycomponent c was added, and mixed via the speed mixer at approximately 22deg. C. for approximately one minute.

Inventive Formulation 8

Inventive Formulation 8 comprises (a) 10.0 g of Dispersion Polymer 1;(b) 0.628 g of CHDA; (c) 0.920 g Acid Catalyst 1; and (d) 1 g of NMP(N-methyl-2-pyrolidone). Components a, b and d were placed in a flask,and mixed using a speed mixer to form a clear solution, and subsequentlycomponent c was added, and mixed via the speed mixer at approximately 22deg. C. for approximately one minute.

Comparative Formulation I

Comparative Formulation I comprises (a) 10.0 g of Dispersion Polymer 1;(b) 0.794 g Acid Catalyst 1; and (c) 1 g of NMP (N-methyl-2-pyrolidone).Components a and c were placed in a flask, and mixed using a speed mixerto form a clear solution, and subsequently component b was added, andmixed via the speed mixer at approximately 22 deg. C. for approximatelyone minute.

Inventive Coated Samples 5 to 8 and Comparative Coated Sample I

Inventive formulations 5 to 8 and comparative formulation A were appliedto a steel substrate via a doctor blade having a a gap of 5 mil, andthen allowed to air dry for 7 days under ambient conditions to form asingle layer Inventive Coated Samples 5 to 8 and Comparative CoatedSample I, respectively. Various standard properties of the CoatedSamples 5 to 8 and Comparative Coated Sample I were tested and reportedin Table III.

Inventive compositions 5 to 8 and Comparative Composition I were appliedto a wood substrate using a foam brush and treated under ambient roomtemperature conditions as indicated below. The wood was coated, driedfor one day, lightly sanded, coated, dried for one day, lightly sanded,coated, and dried for 7 days under ambient conditions before testing.Each Inventive Coated wood sample and comparative coated wood samplewere tested and reported in Table 12.

TABLE 12 Inven- Inven- Inven- Inven- Compar- tive tive tive tive ativeCoated Coated Coated Coated Coated Sample Sample Sample Sample SampleFilm made from 5 6 7 8 8 Stoichiometry 1:1 2:1 0:1 (CHO: Carbarnategroup) p-Toluentsulfonic 1 5 1 5 5 acid (% on soilds) Film Thickness2.27 2.35 2.56 2.54 2.28 (mil) Pendulum 27 36 32 45 24 Hardness (Konig,sec) Pencil Hardness 2B Fail 6B Fail Fail (gouge) 20° Gloss (GU) 58.0818.28 38.74 9.24 35.44 60° Gloss (GU) 99.14 50.34 86.36 21.88 75.76*Water Resistance 4 4 4 3 2 24 h covered water spot test Thickness for2.07 2.02 2.58 2.36 2.45 MEK Resistance 1.82 2.03 2.66 2.18 2.47 NEKResistance 45 55 70 75 25 (hammer, 50 50 65 55 20 double rubs) GelFraction 58.7 62.4 53.8 61.9 0 (%, 24 h, acetone) Stains Wood Substrate7 Day Ambient Dry Skydrol 3 4 4 4 0 Windex 5 5 5 5 3 50% Ethanol 5 5 5 52 Water 5 5 5 5 4

Test Methods

Test methods include the following:

Weight average particle size in nanometers (nm) was determined via lightscattering using a 90-Plus Particle Size Analyzer from BrookhavenInstruments Corporation.

Percent solids is determined by following ASTM D2369-07 (Standard TestMethod for Volatile Content of Coatings (2007)) except as follows.Determinations are done in triplicate. For each determination, weighfrom 0.5 g to 0.7 g of sample of material to be tested into a taredaluminum pan and record weight to 0.1 mg accuracy. Cover sample with 3mL toluene. Place pans into a preheated convection oven at 110° C. for60 minutes, then reweigh to give weight of residual solids. Calculatepercent solids based on weight of residual solids.

Alternatively, percent solids is determined by thermogravimetricanalysis (TGA) by placing 10 mg of sample into a standardthermogravimetric analysis unit that has a nitrogen gas purge. Heat thesample from 25° C. to 300° C. at a heating rate of 10° C. per minute (°C./min). From a graph of % weight loss as a function of time curve, usebreak in slope of the curve where the weight loss levels out as thepercent (fraction of) solids.

Thickness of the Coating:

ASTM D7091-05 (Standard Practice for Nondestructive Measurement of DryFilm Thickness of Nonmagnetic Coatings Applied to Ferrous Metals andNonmagnetic, Nonconductive Coatings Applied to Non-Ferrous Metals(2005)).

Hydroxyl Number:

Determined by following ASTM D4274-05 (Standard Test Methods for TestingPolyurethane Raw Materials: Determination of Hydroxyl Numbers of Polyols(2005)) and is expressed as number of milligrams of potassium hydroxide(KOH) per gram of test substance (mg KOH/g).

Gloss:

measurements are made with a BYK Labotron Gloss Unit following ASTMD523-08 (Standard Test Method for Specular Gloss (2008)).

Impact Resistance:

is determined by using a Gardner impact tester and following ASTMD2794-93 (Standard Test Method for Resistance of Organic Coatings to theEffects of Rapid Deformation (Impact) (1993)).

Abrasion Resistance:

using a Taber abrader (CS-17 wheels, 1000 g weights, 500 cycles).

Pendulum Hardness:

according to the Konig pendulum hardness test by following ANSI ISO1522(Pendulum damping test).

Pencil Hardness:

ASTM D3363-05 (Standard Test Method for Film Hardness by Pencil Test(2005)).

Acid Etch Resistance:

Determined by placing drops of a 10% solution of H₂SO₄ on a surface of acoating, waiting for 2 hours, observing visual effect on the coating andcategorizing the visual effect as either no effect, moderate etch, orsevere etch. No effect means no change to coating surface, moderate etchmeans whitening of the coating surface, and severe etch means blisteringof the coatings surface.

Water penetration resistance: (of a coating) Determined by placing dropsof deionized water on a surface of a coating, covering the drops with aglass cover, waiting for 24 hours, observing visual effect on thecoating, and categorizing the visual effect as either no effect,moderate etch, or severe etch. No effect means no change to coatingsurface, moderate etch means whitening of the coating surface, andsevere etch means blistering of the coatings surface. Assign a relativerating of from 1 to 6, with 6 being highest water resistance and 1 beinglowest water penetration resistance, characterized as follows:

1=Cut through, dissolves coating, cracks/peels away.

2=Water corrodes substrate.

3=Severe blushing, forms bubbles/wrinkles.

4=Mild blushing/yellowing, no change to tou

5=No effect, visible or otherwise.

6=No effect, never even blushed.

Solvent Resistance or MEK Test:

(of a coating) Reported as the number of methyl ethyl ketone (MEK) backand forth rubs that are required to remove enough of the coating down toand thereby exposing the surface of the substrate.

Solubility of the Polyaldehyde in Water:

ASTM E1148-02 (Standard Test Method for Measurements of AqueousSolubility (2002)).

Cross-Hatch Adhesion:

ASTM D3359-09 (Standard Test Methods for Measuring Adhesion by TapeTest) (scale 0B to 5B with 5B being the best adhesion).

Stain Resistance:

(of the coating) R is determined by placing drops of the insult material(water, 50% ethanol/water, skydrol, and windex) onto a piece ofabsorbant paper that is in direct contact with the coating surface,covering the thoroughly wetted paper with a glass cover, waiting for 24hours, observing visual effect on the coating, and categorizing thevisual effect as either no effect, moderate etch, or severe etch. Noeffect means no change to coating surface, moderate etch means whiteningof the coating surface, and severe etch means blistering of the coatingssurface. Assign a relative rating of from 1 to 6, with 6 being the mostsevere damage and 1 being lowest with no affect to the coating,characterized as follows:

1=Cut through, dissolves coating, cracks/peels away.

2=Water corrodes substrate.

3=Severe blushing, forms bubbles/wrink

4=Mild blushing/yellowing, no change to

5=No effect, visible or otherwise.

6=No effect, never even blushed.

Gel Fraction:

(of the coating material) Reported as the % of a film sample thatremains after 24 hours of exposing a polymer film in a Soxletextractorwith refluxing acetone. A film sample is prepared using the sameformulation as the coating and is pored into an aluminum foil boat tomake a dried coating thickness of ˜0.1 mm. The cured film is pealed fromthe foil and ˜1 g of film is placed into a Soxhlet extractor thimble andan accurate weight is recorded. The thimble/film sample is paced into aSoxhlet extactor using acetone as the refluxing solvent. The sample isextracted for 24 hours using the refluxing acetone. The thimble/filmsample is removed, allowed to dry overnight and weighed. The percent ofmaterial remaining after the extraction is calculated.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.

We claim:
 1. A crosslinkable composition comprising: an aqueousdispersion comprising; water; a polycarbamate comprising at least anaverage of 2.0 carbamate functional groups; a polyaldehyde comprising atleast two aldehyde groups; and an acid catalyst; and optionally one ormore surfactants; wherein said aqueous dispersion has a pH in the rangeof less than
 7. 2. The crosslinkable composition of claim 1, whereinsaid composition is capable of being crosslinked at a temperature in therange of less than 80° C.
 3. The crosslinkable composition of claim 1,wherein said composition is capable of being crosslinked at atemperature in the range of less than 40° C.
 4. The crosslinkablecomposition of claim 1, wherein said aqueous dispersion has a pH in therange of less than
 4. 5. A crosslinkable composition of claim 1, whereinthe said aqueous dispersion remains a stable dispersion for at least 30days, while remaining suitable for its intended purpose
 6. Acrosslinkable composition of claim 1, wherein the said aqueousdispersion is heat stable at 60 C for a period of 10 days, whileremaining suitable for its intended purpose
 7. The crosslinkablecomposition of claim 1, wherein said composition is capable of beingcrosslinked upon substantial removal of water.
 8. The crosslinkablecomposition of claim 1, wherein the polycarbamate is the condensationproduct of one or more polyols with an unsubstituted carbamic acid alkylester or urea.
 9. The crosslinkable composition of claim 8, wherein thepolyol is an acrylic, styrene-acrylic, styrene-butadiene,ethylenevinylacetate, vinylacetate, vinyl, saturated ester, urethane,alkyd, ether or carbonate polymer or oligomer thereof.
 10. Thecrosslinkable composition of claim 1, wherein the polycarbamate hascarbamate groups and hydroxyl groups in a ratio of the equivalents ofcarbamate groups to the number of equivalents of hydroxyl functionalgroups of from 1:10 to 20:1.
 11. The crosslinkable composition of claim1, wherein the polycarbamate is prepared via free radical emulsion orsuspension addition polymerization of one or more α,β-ethylenicallyunsaturated monomers at least one of which comprises carbamatefunctionality.
 12. The crosslinkable composition of claim 1, wherein thepolyaldehyde has from 2 to 20 carbon atoms.
 13. The crosslinkablecomposition of claim 1, wherein the polyaldehyde has greater than 20carbon atoms, with the proviso that a polyaldehyde having greater than20 carbon atoms has at least one aldehyde group for every 30 carbonatoms.
 14. The crosslinkable composition of claim 1, wherein thepolyaldehyde is selected from the group consisting of(cis,trans)-1,4-cyclohexanedicarboxyaldehydes,(cis,trans)-1,3-cyclohexanedicarboxyaldehydes, glutaraldeyde, glyoxal,combinations thereof, and/or mixtures thereof.
 15. The crosslinkablecomposition of claim 1, wherein the acid catalyst has a pKa of less than6.0.
 16. The crosslinkable composition of claim 1, wherein the acidcatalyst has a pKa of less than 4.0
 17. The crosslinkable composition ofclaim 1, wherein the acid catalyst is Lewis acid.
 18. The crosslinkablecomposition of claim 1, wherein said composition further comprises acuring inhibitor comprising alcohol.
 19. The crosslinkable compositionof claim 18, wherein said alcohol is selected from the group consistingof ethanol, 1-propanol, 1-butanol, 1-pentanol, Ethylene glycol monoalkylethers, diethylene glycol monoalkyl ethers, propylene glycol monoalkylethers and dipropylene glycol monoalkyl ethers,2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate, combinations thereof,and mixture thereof.
 20. The crosslinkable composition of claim 1,wherein said carbamate functional group has a radical structure offormula of:


21. A crosslinked composition comprising the crosslinked product of thecrosslinkable composition of claim
 1. 22. A process for producing acrosslinkable composition comprising: selecting a polycarbamatedispersion comprising (a) a polycarbamate comprising at least an averageof 2.0 carbamate functional groups, (b) water, and (c) an acid catalyst;selecting a polyaldehyde comprising at least two aldehyde groups;contacting said polycarbamate dispersion with said polyaldehyde in thepresence of said water; thereby forming an aqueous dispersion, whereinsaid aqueous dispersion has a pH in the range of less than
 7. 23. Aprocess for producing a crosslinkable composition 22, wherein the acidcatalyst is a functional group which is incorporated into the backboneof the polycarbamate.
 24. A process for producing a crosslinkablecomposition comprising: selecting a polycarbamate dispersion comprisinga polycarbamate comprising at least an average of 2.0 carbamatefunctional groups, and water; selecting a polyaldehyde comprising atleast two aldehyde groups; selecting an acid catalyst; contacting saidpolycarbamate dispersion, polyaldehyde, and acid catalyst in thepresence of said water; thereby forming an aqueous dispersion, whereinsaid aqueous dispersion has a pH in the range of less than 7.